Pyrazolone pigments

ABSTRACT

PYRAZOLONE PIGMENTS OF THE FORMULA   ((1-R1,4-((-A-NH-)&gt;C=),5-(O=)-2-PYRAZOLIN-3-YL)-CO-NH)2-R,   AND ((3-R3,4-((-A-NH-)&gt;C=),5-(O=)-2-PYRAZOLIN-1-YL)-   CO-NH)2-R   IN WHICH A REPRESENTS A HETERCYCLIC RING FUSED TO AT LEAST ONE BENZENE RING, R REPRESENTS A DIRECT BOND OR AN ORGANIC RESIDUE, R1 REPRESENTS A HYDROGEN ATOM, OR AN ALKYL OR ARYL GROUP, R3 REPRESENTS AN ALKYLENE OR ARYLENE RESIDUE AND R3 REPRESENTS AN ALKYL OR CARBOXYLIC ACID ESTER GROUP, ARE VALUABLE PIGMENTS COLORING PLASTICS AND LACQUERS IN FAST YELLOW TO RED SHADES.

United States Patent 3,780,057 PYRAZOLONE PIGMENTS Christoph Frey, Oberwil, Basel, Switzerland, assignor to Ciba-Geigy AG No Drawing. Filed Aug. 19, 1970, Ser. No. 65,332 Claims priority, applicaitiozizf/wigtzerland, Sept. 2, 1969,

-- rm. c1. co /d 49/14, 57/00 US. Cl. 260310 A 5 Claims ABSTRACT OF THE DISCLOSURE Pyrazolone pigments of the formula roonn -n-Nno o-in in which A represents a heterocyclic ring fused to at least one benzene ring, R represents a direct bond or an organic residue, R represents a hydrogen atom, or an alkyl or aryl group, R represents an alkylene or arylene residue and R represents an alkyl or carboxylic acid ester group, are valuable pigments coloring plastics and lacquers in fast yellow to red shades.

3,780,057 Patented Dec. 18, 1973 Fee This invention is based on the observation that new and valuable pyrazolone pigments of the formula halide of the formula A iJ=o---c-o0Ha1 A =C----CR (U) NH) oil ii NH) 0 N it: M iii-(JOHN (4) with a diamine in a molar ratio of 2: 1.

Since the products of the invention are pigments, they must not contain groups imparting solubility in water, especially acidic groups imparting solubility in water, for example, sulphonic acid or carboxylic acid groups.

Within this class of compounds are included pyrazolone pigments of the formula X; conn-nQ-nnoo X is hydrogen;

Y; is halogen, nitro or methoxybenzolylamino;

X is hydrogen or halogen;

X, and Y each is hydrogen, halogen, lower alkyl, or 5 lower alkylsulphonyl;

R is lower alkyl or lower carhalkoxy;

, v in which X and Y each represents hydrogen, halogen,

lower alkyl or lower alkoxy or in which X represents hydrogen, halogen, lower alkyl, or lower alkoxy.

I The starting materials used are preferably carboxylic acid chlorides of the formulae in WhiChX Y and X each represents a hydrogen or a halogen atom, an alkoxy group, a carboxylic acid amide group or a nitro group, X and Y each represents a hydrogen or a halogen atom or an alkyl, alkoxy, alkylsulphonyl, nitro or acylamino group and R represents an alkyl or a car-balkoxy group.

The carboxylic acids are advantageously btained by condensing a pht'halimidine hydrochloride yvith the correspondingphenylpyraiolone carboxylic acid. 1

Compounds that are also of interest as starting materials are the carboxylic acid chlorides of the formulae Qixi | or i in which X Y X' ,'Y R and X have the meanings givenralaove. A I i The correspondingcarboxylic acids are advantageously obtained by condensing a compound of the formula X1 I X1 Q $O,-scHs n or .N.HJ

Y} I 1 i w p with the corresponding phenylpyrazolone carboxylic acid.

The compounds of Formulae 9 and 10 are advantageously obtained by heating naphthostyryl or a nuclearsubstituted derivative thereof, for example, 4-chloronaphthostyryl, 2-methoxynaphtho'styryl, 5-'methoxyna'phthostyryl, or 4-bromonaphthostyryl, with phosphorus pentasulphide in pyridine and methylating the resulting thionaphthostyryl with methyl iodide.

Conversion of the carboxylic acids into their halides can be efiected in the usual manner by a treatment with acid halogenating agents, especially thionyl chloride. The

treatment with the said acid halogenating agents is advantageously carried out in an inert organic solvent, for example, dimethylformamide, a chlorobenzene, for example, monochlorobenzene or dichlorobenzene, toluene, xylene or nitrobenzene. If necessary, dimethylformamide may be used in conjunctionwvith the last five solvents specified.

The diamines to be used in accordance with the invenvention are, for example, hydrazine or aliphatic diamines, for example, ethylene diamine, heterocyclic diamines, but preferably aromatic diamines and especially those of the benzene, diphenyl or naphthalene series. Specially interesting are the diamines of the formula in which X, Y and Z each represents a hydrogen or a halogen atom or an alkyl or alkoxy group.

The following diamines are given as examples:

1,2-diaminobenzene, 1,2-diamino-4-nitrobenzene, 1,3-diaminobenzene, 1,3-diamino-2-methylbenzene, 1,3-diamino-4-methylbenzene, 1,3sdiamino-4-chlorobenzene, l,3-diamino-2,6-dimethylbenzene, 1,3-diamino-4,6-dimethylbenzene, 1,3-diamino-2,5-dichlorobenzene, 1,3-diamino-4,6-dichlorobenzene,

' 1, 3-diamino-4,5,6-trichlorob enzene,

1,3-diamino-S-carbomethoxybenzene, 1,3-diamino-5-carbanilidobenzene, 1,4-diaminobenzene, 1,4diamino-2-ch1orobenzene, 1,4diamino-2-bromobenzene, 1,4-diamino-2,5-diehlorobenzene,

l,4ediaminos2rmethylbenzene, 1,4-diamino-2,S-dimethylbenzene, 1,4 diamino z-methoxybenzene, 1,4-diamino-2,S-dimethoxybenzene, 1,4-diamino-2,S-diethoxybenzene, 1,4-diamino-2-chloro-S-methylbenzene, 1,4-diamino-2-chloro-S-methoxybenzene, 1,4-diamino-2methyl-5-methoxybenzene, 4.4'-diaminodiphenyl, 3,3-dichloro-4,4-diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl, 3,3-dimethoxy-4,4'-diaminodiphenyl, 3,3,5,5-tetrachloro-4,4'-diaminodiphenyl, 2,2'-5,5'-tetrachloro-4,4'-diaminodiphenyl, 3,3'-dichloro-5,5-dimethyl-4,4f-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 4,4-diaminodiphenylketone, 4,4'-diaminodiphenylsulphone, 3,3-diaminodiphenylsulphone, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-diamino-4,4'-dimethyldiphenylmethane, 3,3'-diamino-4,4-dichlorobenzyl, 4,4'-diamino-2,5,2,5'-tetrachlorodiphenylurea, di-(4-aminobenzenesulphonyl)-methylimide, 4- (4-aminob enzoylamino )-aminobenzene, 4,4'-diaminodiphenylformylamine, 4aminobenzoic acid-4-aminophenyl ester, 2,8-diaminochrysene, 3,8-diaminopyrene, 3,10-diaminopyrene, 4,1 l-diaminofiuoroanthene, 2,6- or 1,5-diaminonaphthalene, 2,6-, 1,4- or 1,5-diaminoanthraquinone, diaminobenzthiazoles,

for example,

2- 4'-aminophenyl) -6-aminob enzthiazole, 2,6-diaminopyridine, 2,6-diaminopyrimidine, 3,5-diamino-1-methyl-2,4,6-triazine and 3,3-diaminodib enzofurane.

Condensation between the carboxylic acid halides defined above and the diamines is advantageously carried out in an anhydrous medium. Under these conditions it generally proceeds surprisingly easily, even at temperatures within the boiling range of the common organic solvents, for example, toluene, monochlorobenzene, di-

chlorobenzene, trichlorobenzene, nitrobenzene and the like. To accelerate the reaction, it is generally advantageous to use an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the products obtained are crystalline and some are amorphous and they are generally obtained in a very good yield and in a pure state. It is expedient first to isolate the acid chlorides obtained from the carboxylic acids. In some cases, however, isolation of the acid chlorides may be omitted without harm and condensation may be carried out immediately after preparation of the carboxylic acid chlorides.

The new products are valuable pigments that can be used for a very wide variety of purposes. For example, they may be used in a finely divided form for the spincoloration of filament and stable-fibre viscose, cellulose ethers and esters, polyamides, polyurethanes and polyesters, and in the production of coloured lacquers and lake-formers,solutions or products'made from cellulose acetate, nitrocellulose, natural or synthetic resins, for example, polymerisation resins or condensation resins, for example, aminoplasts, alkyld resins, and phenoplasts, and also polyolefines, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, rubber, casein, silicones and silicone resins. They may also be used advantageously in the manufacture of coloured pencils and laminated sheet material.

The following examples illustrate the invention, the parts and percentages being by weight, unless otherwise stated.

EXAMPLE 1 36 parts of 2-methylmercaptobenzo[c,d]-indolehydroiodide are dissolved in 150 parts of pyridine while stirring. 20.4 parts of l-phenyl-5-pyrazolone-3-carboxylic acid are added and the batch is heated to to C. It is kept at that temperature for 1% hours, allowed to cool to 60 C., diluted with 160 parts of methanol and cooled to 15 to 20 C. The dyestutf carboxylic acid that precipitates is isolated by filtration, washed with methanol and water and dried in vacuo at 90 to 100 C.

To prepare the acid chloride, 28 parts of the above acid are stirred into 130 parts of anhydrous orthodichlorobenzene and the batch is heated to 90 to 100 C. 13 parts of thionyl chloride are then added dropwise and the batch is heated for 3 hours at to C. The reaction mixture is cooled and filtered, the filter residue is washed with anhydrous benzene and the acid chloride so obtained is dried in vacuo at 60 C.

7.47 parts of the carboxylic acid chloride of the formula so obtained are heated to 100 to 110 C. in 170 parts of anhydrous ortho-dichlorobenzene and 0.05 part of thionyl chloride. A solution of 2.44 parts of 3,3'-dimethoxy-4,4'-diaminodiphenyl and 0.8 part of pyridine in 50 parts of anhydrous ortho-dichlorobenzene having a temperature of 100 to 110 C. is added and the batch is heated for 12 hours at to C. The batch is allowed to cool to 100 C., filtered, the filter residue is washed with ortho-dichlorobenzene having a temperature of 110 to 130 C. until the washings run colourless, the orthodichlorobenzene is displaced with methanol and water and the pigment obtained is dried in vacuo at 90 to 100 C. A dark red powder is obtained that produces a brownish red film possessing food fastness to migration and light when worked into polyvinyl chloride on a roller mill.

The 2-methylmercaptobenzo[c,d]-indole-hydroiodide specified in the first paragraph above can be prepared in the following manner:

89 parts of naphthostyryl and 60 parts of phosphorus pentasulphide are refluxed for 75 minutes at 110 to 114 C. in 250 parts of anhydrous pyridine. The reaction solution is cooled, poured into 1,250 parts of hot water'and kept for one hour at 90 to 95 C. while stirring. The thionaphthostyryl so obtained is allowed to cool, isolated by filtration, washed well with water and then recrystallized in alcohol.

37 parts of thionaphthostyryl and 34 parts of methyl iodide are kept at the boil for 90 minutes in parts of acetone. The batch is cooled, the Z-methylmercaptobenzo [c,d]-indole-hydroiodide is isolated by filtration, washed with a small amount of acetone and then dried in vacuo at 30 to 40 C.

The following table lists components from which further pigments may be obtained by condensing a carbostyryl derivative listed in Column I with a pyrazolone derivative listed in Column II according to the procedure described in the above example, converting the carboxylic acid obtained into the acid chloride, and condensing the acid chloride with a diamine listed in Column HI in a molar ratio of 2: 1. Column IV indicates the shade produced by the pigment so obtained in polyvinyl chloride.

36.5 parts of iminophthalimidine hydrochloride and 41 parts of 1-phenyl-5-pyrazolone-3-carboxylic acid are refluxed for 30 minutes in 500 parts of ethylene glycol monomethyl ether. After cooling, the batch is filtered and the filter residue is washed with methanol and water. The dye stufi carboxylic acid of the formula is obtained.

To form the acid chloride, 33.3 parts of the above acid 5 residue is washed with anhydrous benzene and dried in L .y v. u W I TABLEContinued I I ,II III IV 31 Same as Example 30 Same as Example 30 1,4-diamino-2,5-dichloroben2ene-; Brown. i "-0111 1,3-diamino-4,6-dimethylbenzene Claret;

N 0 N h i -COOH 33...:; Same 8S 8b0VB-.;;:;::'.-.:::.:;.:- Sameasabove--;;.;-:.. 1,5-dlamino-napthalene----;;:;;-...;-;-;:.:.;:;: D0.

34 do wUl -CH; 1,4-diamino-2,5-dlehlorobenzene Red.

35.,.-.-.;.-.-. do Same as above...-.--.'.-.-.-.-.... 1,4-diamin0-2,5-dimethoxybenzeue..;;.;.;.:::;:;; Red; 36 d0 3,3-dichloro-4,4-diaminodiphenyl Red. 37 o N 3,3-dimethoxy-4,4-diamlnodiphenyl Red- 4 L i COOH :.-..do Orange.

30 (in Same asabove-.;;.';..;.:;:;:;. 2,5-dimethoxy-1,4-diaminobenzene-.;;;.;..;;:.... Reddish orange. 4 do 1 do 2,5-dichloro-1,4-diaminobeuzene Orange- 41 a FI-OOOH 3,3'-d1chloro4,4-diaminod1phenyl Brown:

42 d0 1,3'diamlno-4-methylbenzene..;:---;:-;...--;-;-;-; Orange. 4'; do do 4,4'-diaminoazobenzone Orange red- 44 d do 4,4'-dlamino-2,2-dimethylazobenzene Do.

EXAMPLE 2 20 and 0.5 part of dimethylforrnamide are heated to to C. in parts of anhydrous ortho-dichlorobenzene. 16 parts of thionyl chloride are then added dropwise, and the batch is kept at that temperature for 3 hours while stirring. The batch is cooled to 20 C., filtered, the filter vacuo at 60 C.

7.03 parts of the dyestufi carboxylic acid chloride so obtained are heated to 100 to 110 C. while stirring in 170 parts of anhydrous ortho-dichlorobenzene after the addition of 0.05 part of thionyl chloride. A warm solution of 1.57 parts of 2-methyl-5-chloro-1,4-diaminobenzene in 50 parts of anhydrous ortho-dichlorobenzene is added and the batch is heated for 16 hours at to C. The orange-red pigment that precipitates is isolated by filtration while hot and well washed with hot ortho-dichlorobenzene, methanol and water. It is then dried in vacuo at 100 C., and an orange-red powder is obtained that produces an orange film possessing very good fastness to migration and light when worked into polyvinyl chloride on a roller mill.

15 16 TABLECoutinued 1 'II' III N 5'6 -I COOH 3,3-diehloro-4,4'-d1amlnodiphenyl;;.z Brown. H

CH O NH Co '.-...-do 1, 4-dlamlno-2, 5-dlchlorobenzene Brown;

I \C=NH ;j 7,} QT .HCl

58. Same as abov 3,3-dlmethoxy-4.4'-diamlnodlphenyl D0.

EXAMPLE 3 ment obtained in accordance with the first three parah ma tobenzo c d indole of the graphs of Example 1 and then worked to and fro tor 7 f of t e e p 1 minutes at 140 C. on a two-roller mill. A bI'OWlJlSh red film possessing very good fastness'to light and migration 0 is obtained =3 O 0 SH EXAMPLE 5 ll N 0 NH 0.25 part of the pigment obtained 1n accordance with and 25.8 parts of 1-(2'-chloro-5'-carboxyphenyl)-3-meththe first thre? PaTagYaPhS of Example 40 Parts of an y1 5 pyrazo1one are heated for 2 hours at 170 to alkyd-melamine stoving lacquer havi nga SOlIdS content in 100 parts of nitrobenzene while stirring. After cooling of Parts of mamum dfoxlde are ground the reaction mixture, the dyesmfl of the formula a rod mill for 24 hours. A thin coating of the lacquer is applied to aluminium foil and stoved for one hour at 120 @c==-C-CCH: 40 C. A brownish red coating possessing excellent fastness to II light is obtained.

l oc': N v 0 AM Eji 100 parts of polyethylene ter ephthalate chips are mixed C1 with 1 part of the pigment obtained 'in accordance with the first three paragraphs of Example 1. The chips are then spun into filaments at about 270 C. in the usual manner. The polyester filaments so obtained are coloured reddish brown and possess good properties of fastness.

is isolated by filtration, well washed with methanol and water and then dried in vacuo at 100 C.

The carboxylic acid is converted into the acid chloride in the manner described in Example 1 and then condensed EXAMPLE 7 with 1 3-diamino-4 6-dimethylbenzene. The pigment s0 ob- 100 parts of a caprolactam polyamide 1n the form of tameld 11s ldentical with pigment N0. 32 m the table 1n EX chips are ed with 1 part of the P g No. 18 in the amp 6 table in Example 2 in a mixing drum; The chips are then Pigment No. 33 in the table in Example 1 can be prepared inthe same manner spun into filaments by the melt-spinning process customarily used for polyamides'. The reddish o'rangepolyamide EXAMPLE 4 fibres so obtained possess very good fastness to light.

A mixture is prepared from parts of polyvinyl chlo- I claim: I ride, 35 parts of dioctyl phthalate and 0.2 part of the pig- 0 1. A pyrazolone pigment of the formula x; Y x, Y;

I X3 0 NH-R-NHC O--Xa in which in which X, is hydrogen; X is hydrogen; Y is halogen, nitro or methoxybenzoylamino; Y s halogen, mtro or methoxybenzoylammo; X i h d or h l X and Y each is hydrogen, halogen, lower alkyl, lower X and Y2 h i hydrogen, h l lower alkyl, or lower alkoxy, lower alkylsulphonyl, nltro or lower alkanoylalkylsulphonyl; 1 f R is lower alkyl or lower carbalkoxy; R 15 Ris in which X and Y each represents hydrogen, halogen, lower alkyl or lower alkoxy or in which X and Y each represents hydrogen, halogen, lower alkyl, or lower alkoxy or in which Z represents hydrogen, halogen, lower alkyl,

or lower alkoxy. 1 a in which Z represents hydrogen, halogen, lower alkyl, 2. A pyrazolone pigment of the formula or lower alkoxy.

X1 Y1 X1 Y1 o= =c-0-0 ONH-R-NHO OCO= i=0 NH 0= l1 l1 N 3. The compound of claim 1 of the formula q 11 01 o C0 NH NH JO 0 4. The compound of claim 1 of the formula o N/ n F; Fac- 3,780,057 19 20 5. The compound as claimed in claim 1 of the formula (JO-NH NH-CO References Cited UNITED STATES PATENTS 1,991,313 2/1935 Bonhote et a1. 260-310A 1,999,438 4/1935 Bonhote et a1. 260310A 2,254,354 9/1941 Davies 260310A 2,589,004 3/1952 Weissbergeret a1. 260310A FOREIGN PATENTS 159,665 4/1933 Switzerland 260-310 A 161,739 7/ 1933 Switzerland 260-310 A 161,740 7/1933 Switzerland 260-310 A 161,741 8/1933 Switzerland 2603 10 A 161,742 8/1933 Switzerland 260-310 A 161,743 8/1933 Switzerland 260-310 A NATALIE TROUSOF, Primary Examiner US. Cl. X.R.

854.2, 162R, 162 S, 172, 178 R, 178 E, 179; 106-148, 165, 193 D, 193 P; 260-37 SB, 37 N, 37 P, 38, 39 P, 40 R, 41 C, 326.9, 571, 575, 762 

